Tuning the thermotropic and lyotropic properties of liquid-crystalline terpyridine ligands

被引:41
作者
Camerel, Franck
Donnio, Bertrand
Bourgogne, Cyril
Schmutz, Marc
Guillon, Daniel
Davidson, Patrick
Ziessel, Raymond
机构
[1] Univ Strasbourg, CNRS UMR 7509, Ecole Chim Polymeres Mat, Lab Chim Mol, F-67008 Strasbourg, France
[2] Univ Strasbourg, CNRS UMR 7504, Inst Phys & Chim Mat Strasbourg, Grp Math Organ, F-67034 Strasbourg 2, France
[3] Inst Charles Sadron, CNRS UPR 22, F-67083 Strasbourg, France
[4] Univ Paris 11, Phys Solides Lab, UMR 8502 CNRS, F-91405 Orsay, France
关键词
amphotropic; gelator; hydrogen bonds; liquid crystals; mesogenic ligand; terpyridine;
D O I
10.1002/chem.200501431
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A rational synthetic strategy is developed to provide compact and simple terpyridine (terpy) mesogens that show liquid-crystallinity both as pure compounds and in organic solution (amphotropic compound). The use of a central 4-methyl-3,5-diacylaminophenyl platform equipped with two lateral aromatic rings, each bearing three appended aliphatic chains, allows connection of a 2,2 ':6 ',2 ''-terpyridine fragment through a polar group such as an ester, amide, or flat conjugated alkyne linker. For the T(12)ester and T(12)amide scaffolds, the mesophase is best described as a lamellar phase, in which the molecules self-assemble into columnar stacks held together in layers. In the T(12)amide case, the additional amide link results in significant stabilization of the lamellar phase. The driving forces for the appearance of columnar ordering are the hydrogen-bonding interactions of the amide groups, which induce head-to-tail pi-stacking of the terpy subunits. Replacing the polar linker by a nonpolarized but linear alkyne spacer, as in the T(12)ethynyl compound, provides a columnar meso-phase organized in a rectangular lattice of p2gg symmetry. In this arrangement, two nondiscotic molecules arranged into dimers by hydrogen bonding and pi-pi stacking pile up in a head-to-tail manner to form columns. In addition, the T 12 amide compound proves to be an excellent gelator of cyclohexane, linear alkanes, and DMSO. The resulting robust and transparent gels are birefringent and formed by large aggregates that are readily aligned by shear-flow. TEM and freeze-fracture microscopy reveal that the gels have an original layered morphology made of fibers.
引用
收藏
页码:4261 / 4274
页数:14
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